Quaternized azo dyestuffs containing triazolium phenyl groups



United States Patent Int. Cl. (30% 29/08, 29/28, 23/36 U.S. Cl. 260-155Claims ABSTRACT OF THE DISCLOSURE Diazo components such asl-(aminophenyl)-triazole& (1,2,3) and their nonionic substitutionproducts and quaternary salts are diazotised and coupled to produce azodyestuifs which are adapted for use in dyeing fibers and fabrics ofpolyacrylonitrile, copolymers of acrylonitrile and dicyanoethylene,cellulosic fibers, silk, and leather, which dyestuffs correspond to theformula:

wherein A and B stand for a residue of a coupling component, R standsfor an alkyl radical with 1-4 carbon atoms or for benzyl, R stands for anonionic substituent,

m is 0-3, n is 0 or 1, and X is an anion.

In the above formula R denotes an alkyl radical with 14 carbon atoms ora benzyl radical, R stands for a nonionic substituent, A and B are theradicals of coupling components, m is the number 0, 1 or 2, n is thenumber 0 or 1, and X- is an anion. 1

It has not yet clearly been proved whether the alkyl radical or thebenzyl radical R stands in the 2- or 3-position of the triazole ring ofthe dyestuffs of the general Formula I. With the greatest probabilitythe radical R is present at the 3-positioned nitrogen atom of thetriazole mug.

of the non-ionic substituents R the following should be mentioned inparticular, halogen, alkyl, trifiuoroalkyl, alkoxy and thioetherradicals, the alkyl radicals containing 1-4 carbon atoms.

The radicals of the coupling components A and B are preferably those ofthe S-pyrazolone, S-aminopyrazolone, phenol, aminobenzene, naphthol oraminonaphthalene series, as well as other radicals of the heterocyclicseries, especially of the quinoline series. The cationic dyestutf3,519,615 Patented July 7, 1970 radical is, by definition, free fromsulphonic acid groups. The new azo dyestuffs are prepared in such a waythat the diazonium compound of an amine of the formula wherein R R m andX- have the same meaning as above, is combined with a couplingcomponent, optionally further diazotised and again coupled with an azocomponent, selecting the starting components free from sulphonic acidgroups.

The dyestulfs according to the invention may also be produced in such amanner that azo dyestufis of the general formula (Rz)m (III) wherein RA, B, m and n have the same meaning as above, are treated withalkylating agents R X, while quaternising the 2- or 3-positionednitrogen atom of the triazole ring.

Diazo components suitable according to the present process arel-(aminophenyl)-triaz0les-(1,2,3) and their non-ionic substitutionproducts as well as their quaternary salts. These compounds can beproduced by reacting nitrophenylazides with acetylene tol-(nitrophenyl)-triazoles- (1,2,3) and reducing these to the amines.From the amines there are obtained by acetylation and subsequentalkylation the quaternary salts which are converted into the amines ofthe Formula II by hydrolysis with mineral acids. Alkylating agents whichmay be used for this purpose are the following, for example, methylchloride, methyl bromide, methyl iodide, benzyl chloride,trimethyloxonium-borofluoride, dimethyl sulphate, diethyl sulphate andp-toluene-sulphonic acid methyl, -ethyl, or -butyl esters. When the1-(acetylaminophenyl)-triazoles-(1,2,3) are alkylated, it is mostprobable that the alkyl radical becomes attached to the nitrogen atom 3of the triazole ring.

The diazotisation of the diazo component (II) is effected according toknown methods, for example in an aqueous, mineral acid solution withsodium nitrite.

Suitable diazo components are the following, for example:

l- (4-aminophenyl) -triazole-=( 1,2,3

l- 3 -aminophenyl) -triazole- 1,2,3),

1-( 3-chloro-4-aminophenyl) -triazole-( 1,2,3

1- 3'-methyl-4-aminophenyl -triazole-( 1,2,3),

1- 2'-methyl-4'-aminophenyl) -triazole-( 1,2,3),

1- 2-chloro-4-aminophenyl -triazole- 1,2,3),

l-( 3 '-methoXy-4-aminophenyl) -triazole- 1,2,3

1- 3 '-methylthio-4-aminophenyl) -triaz0le-( 1,2,3 1-(2'-methoxy-4'-aminophenyl) -triazole- 1,2,3 1-(2'-methylthio-4'-aminophenyl -triazole- 1,2,3), 1- (3'-propyl-4-aminophenyl) -triazole- 1,2,4),1-(2',51-dimethyl-4'-aminophenyl) -triazole-' 1,2,4) 1(2,5'-dichloro-4'-aminophenyl) -triazole-( 1,2,3)

1- 2-Inethyl-5 '-methoxy-4'-aminophenyl -triazole- (1,2,3),l-(3'-ethoxy-4'-aminophenyl)-triazole-(1,2,3),1-(4-chloro-3'-aminophenyl)-triazole-( 1,2,31-(4'-ethyl-3-aminophenyl)-triazole-(1,2,3), 1-(4'-propoxy-3'-aminophenyl) -triazole-( 1,2,31-(3-chloro-5'-aminophenyl)-triazole-(1,2,3),1-(3-ethyl-5'-aminophenyl)-triazole-(1,2,3 1-3',5-dichloro-4-aminophenyl) -triazole-( 1,2,3) and the quaternary saltsof these compounds which most probably carry the alkyl or benzyl groupat the nitrogen atom 3 of the triazole ring, for example as thefundamental types of the two compounds of the formula Suitable couplingcomponents A-(NH or B are the following, for example: 1-phenyl-3methyl-pyrazolone- (5), l-(fi-cyanoethyl) 3 methyl-pyrazolone-(S),l-(fihydroxyethyl)-3 methyl-pyrazolone (5), 1,3-diphenylpyrazolone-(S),2 methylpyrazolo[2,3-a1benzimidazole,2-methylpyrazolo[3,2-b]quinazolone, phenol, p-cresol, mcresol,3-chlorophenol, aniline, o-toluidine, m-toluidine, 3- chloro-aniline,3-anisidine, Z-anisidine, 1-amino-3-methyl- 6-methoxy-benzene,1-amino-2,5-dimeth0xybenzene, N,N- dimethylaniline, N,N-diethylaniline,N-ethyl-N-B-cyanoethylaniline, N,N-bis-(fl-cyanoethyl)-aniline,N,Nbis-(/3- hydroxyethyl)-aniline, N-methyl-diphenylamine, naphthol-(2), naphthol-(l), l-amino-naphthol-(S), l-3-dihydroxyisoquinoline,Z-methyl-indole, 1-ethyl-l,2,3,4 tetrahydroquinoline, 1,2,3,4tetrahydro-quinoline-propionic acid (1)-ethyl ester, 1,2,3,4tetrahydro-3-hydroxy-benzo[h]- quinoline, 1,2,3,4tetrahydro-3,7-dihydroxy-benzo[h]- quinoline.

Preferred coupling components are as follows: wherein A stands for theresidue of a coupling component selected from a group consisting of (a)aminophenyl which is unsubstituted in the phenyl radical, or issubstituted in the phenyl radical by at least one member selected fromthe group consisting of methyl, ethyl, bromo, chloro, methoxy, ethoxy,acetyla'mino, methylmercapto, and ethylmercapto, and which isunsubstituted at the N atom or is substituted at the N atom by at leastone member selected from the group consisting of lower alkyl, phenyl,hydroxyethyl, cyanoethyl, and benzyl;

(b) hydroxyphenyl which is unsubstituted or is substituted by at leastone member selected from the group consisting of methyl and chloro;

(c) hydroxynaphthalene which is unsubstituted or is substituted by anamino group;

(d) pyrazo1on-(5)-yl which is substituted with at least one memberselected from the group consisting of methyl, phenyl, cyanoethyl, andhydroxyethyl;

(e) 2-methyl-pyrazolo[2,3-a]benzimidazolyl;

(f) 2-methyl-pyrazolo[3,2-b] quinazolyl;

(g) Z-methyl-indolyl;

(h) l,3-dihydroxy-isoquinolyl;

(i) tetrahydrobenzoquinolyl substituted by at least one hydroxy group;

(j) tetrahydroquinolyl which contains at the N atom a substituentselected from the group consisting of ethyl and ethoxycarbonylethoxyradicals;

and wherein B is selected from (a) as defined above.

The coupling of the starting components is effected in known manner, forexample in a neutral, acidic or weakly alkaline, aqueous medium.

If the dyestuffs according to the invention are prepared by alkylationof the dyestuffs of the general Formula III, then the alkylation isexpediently carried out by heating in an inert organic solvent, e.g. inhydrocarbons, such as benzene, toluene or xylene; halohydrocarbons, suchas carbon tetrachloride, ethane tetrachloride, chlorobenzene,o-dichlorobenzene; nitrohydrocarbons, such as nitrobenzene ornitronaphthalene, or in dimethyl formamide, acetonitrile or dimethylsulphoxide with the use of preferably equivalent amounts of alkylatingagents, for example with methyl chloride, methyl bromide, methyl iodide,ethyl bromide, benzyl chloride, trimethyl-oxonium-borofiuoride, dimethylsulphate, diethyl sulphate, p-toluene-sulphonic acid methyl, -ethyl or-butyl ester. In the case Where the starting dyestuffs also containother quaternisable groups than the triazole ring, it may beadvantageous to use larger than equivalent amounts of alkylating agents.

The resulting quaternised dyestuffs are hardly soluble in the solventsemployed and can be isolated by filtration. If the quaternised dyestuffsare dissolved, partly or completely, when using dimethyl formamide,dimethyl sulphoxide or acetonitrile, then they can be separated bydilution with water or by the addition of water-soluble salts, forexample sodium or potassium chloride.

The dyestuffs of the Formula I prepared by coupling the diazoniumcompounds of amines of the Formula II with the stated couplingcomponents, as well as the dyestuffs of the Formula I produced byalkylation of the dyestuffs of the Formula III can be purified bydissolving in water and separation by the addition of water-solublesalts, for example sodium or potassium chloride.

The dyestuffs obtained according to the process of the invention containthe anionic radical X- which is preferably the radical of a strong acid,for example of sulphuric acid or its semi-esters or of an arylsulphonicacid, or an halogen ion. These anions may, however, also be replaced bythe radicals of other acids, for example of phosphoric acid,hydrofluoboric acid, formic acid, acetic acid, tartaric acid or lacticacid. The dyestuff salts may also be converted into double salts bymeans of inorganic salts, for example with zinc chloride. The anions Xmay thus be, for instance, Cl, Br-, CH SO C H SO -3 p-toluensulphonate,benzene sulphonate, phosphate, acetate, formiate, oxalate, lactate,propionate, maleinate, tartrate, N0 1 perchlorate and chloro zincate. Itis to be understood, that the anion X does not affect the tincturialapplicability of the azo dyestuff and is substantially uncoloured asusual in cationic dyes.

The dyestuffs obtained according to the present process are eminentlysuitable for the dyeing and printing of fully synthetic fibres ofpolymers and copolymers of acrylO- nitrile and dicyanoethylene, wherebyfast shades are obtained. The dyestuffs can also be used for the dyeingand printing of tannin-treated cellulose materials, silk and leather.

The following examples are given for the purpose of illustrating theinvention. The parts are parts by weight. The quarternary substituent inthe triazolium salt is throughout indicated in the 3-position of thetriazolium ring, although this position could not be clearly establishedby experiment.

EXAMPLE 1 A solution of 28.6 parts 3-methyl-1-(4'-aminophenyl)-1,2,3-triazolium methosulphate of the formula CH=CH which is obtained bysaponifying at -100 C. for 30 minutes 33 parts3-methyl-1-(4-acetylamino)-l,2,3-triazolium methosulphate in a mixtureof parts water and 30 parts concentrated hydrochloric acid, isdiazotised at 3 C. with a solution of 6.9 parts sodium nitrile in 50water. The clear diazonium salt solution is freed from an parts water.The clear diazonium salt solution is freed excess of nitrous acid bymeans of amidosulphonic acid from a small excess of nitrous acid bymeans of amidoand then added to a solution of 18.3 parts N-methyl-N-sulphonic acid and then added to a solution of 17.4 parts phenylanilinein 50 parts water and 15 parts concentratedN-ethyl-N-(fi-cyanoethyl)anilin in a m r 0f Parts 5 hydrochloric acid.The coupling to the diazo dyestuff, water and 25 parts concentratedhydrochloric acid. which starts immediately, is completed by theaddition of Coupling resulting in the monoazo dyestuff sets in imsodiumacetate; after completion of the coupling, the mediately; it iscompleted by slowly adding a sodium acedyestuff is precipitated by theaddition of 40 parts sodium tate solution and, after completed coupling,the resultchloride and finally filtered off. The dyestuff thus formeding dyestuif is completely precipitated by the addition of has probablythe constitution 50 parts sodium chloride. The dyestuff is then filteredoff and dyes textile articles made of polyacrylonitrile in a and dried.45 parts of a red dyestuff powder are obtained brownish red shade withvery good fastness to wet processwhich readily dissolves in water withan orange colour. 20. i d very good fa tn to i h The dyestuff probablycorresponds to the formula EXAMPLE 8 When the diazonium salt solutionprepared according /C2H5 to Example 1 is added to a finely divideddispersion of CH NN=NN CHSSOF 17.4 parts1-phenyl-3-methyl-pyrazolone-(5) in 250 parts \C2H4CN Water and the pHvalue of the mixture is maintained at and dyes fibres and fabrics ofpolyacrylonitrile from an a yellow dyestufl- 1S obiamed whlch.ls i msual manner by filtratlon. ThlS dyestuff 'Wl'llCh 1s obtalned acidicsolution in yellowish orange shades. The dyeings in a yield of 42 6parts dyes textile materials of poly 2: 55:5 g i gii fastness to WetProcessmg and good acrylonitrile in yellow shades. The dyeings possessvery The 3 y 1 y p y good fastness to wet processing and very goodfastness lium methosulphate was prepared as follows: p-nitroto hght'phenylazide is reacted in an acetone solution at 100 C., EXAMPLE 9 in anautoclave, with acetylene to give 1-(4'-nitrophenyl)- 5 The diazoniumsalt solution prepared according to 1,2,3-triazole (M.P. 208210 C.), thelatter is reduced Example 1 is added to a solution of 15.9 partsl-arnino-S- to l-(4'-aminophenyl)-1,2,3-triazo1e (M.P. 13 9-140 C.)hydroxy-naphthalene in 300 parts water and 20 parts conwith ironhydrochloric acid in water and the amino corncentrated hydrochloricacid. The immediately starting pound acetylated with acetic anhydride inan aqueous p g is Completed, Without ring, i a medium suspension to givel-(4-acetylaminophenyl)-1,2,3-triazo1e which reacts acid to Congo andthe resultant dyestuff is (M.P. 206207 C.). By reacting the acetylaminocomprecipitated by the addition of 40 parts sodium chloride.

pound with dimethyl sulphate in chlorobenzene at 100- Th dyestuff isisolated by filtration. After drying, 43.2 120 C., the 3 methyl 1(4-acetylaminophenyl)-1,2,3- P ts f the dyestulf are obtained.triazolium methosulphate (M.P'. 222-223 C.) is obtained. The dyestllifhas th probable C nstitution With the coupling components set out in thefollowing N table, the diazo component of Example 1 also yields valu-(0% able, water-soluble azo dyestuffs which dye polyacrylo- Hie-N a at)nitrile fibres in the specified shades: O

Shade on E a le Coupling component polyacrylonitrile 2 X mp N N d th 1 TO and dyes textile articles made of polyacrylonitrile 1n lme 8.111 1neran e. 3 2 t 1 1 st l ll i h blulsh Bordeaux Besldes good fastness toWet orange. processmg, the dyeings have a very good fastness to light.3-methyl-N,N-dlmethylamlme. Orange. 3-chl0ro-N,N-dimethylaniline..Yellowish orange. EXAMPLE 10 6 N-methyl-N-phenylaniline Do. 5

EXAMPLE 7 If in Example 9 there is used as coupling component, insteadof l-arnino 5 -hydroxy-naphthalene, 21.5 parts The diazonium saltsolution prepared according to Ex- 1,2,3,4 tetrahydro 3,7dihydroxy-benzo[h]quinoline, ample l is added at 0l0 C. to a solution of10.7 parts then 48.7 parts of a blue dyestutf powder are obtained3-methylaniline in 50 parts water and 10 parts concenwhich dyes textilematerials of polyacrylonitrile in violet trated hydrochloric acid andthe coupling which sets in shades. The dyestufi has the probableconstitution immediately is completed by adjusting the pH value to Thedyeings are very fast to wet processing and to light. 45 by means ofsodium acetate. The dyestufi is precipitated by the addition of 30 partssodium chloride and EXAMPLE 11 filtered off. It is a yellow-brownpowder. This powder is 19.5 Pa 1 chloro aminophenyh-triazoledissolved in300 parts water, mixed with 25 parts conare dissolved in 100 Parts Watercontaining 25 centrated hydrochloric acid and diazotised at 38 C. partsconcentrated hydrochloric acid and the solution is with a solution of6.9 parts sodium nitrite in 50 parts diazotised at 0-3 C. with asolution of 6.9 parts sodium nitrite in 40 parts water. After removal ofa possibly present excess of nitrous acid with amidosulphonic acid, theclear diazonium salt solution is added to a solution of 13.5 parts3-methyl-N,N-dimethylaniline in 100 parts water and 10 partsconcentrated hydrochloric acid. The coupling resulting in the monoazodyestuff sets in immediately and is completed by buffering by means ofsodium acetate. The resultant dyestuff is filtered off and Washed. Afterdrying, 31.7 parts are obtained. The dyestulf has the formula N /CHs Hi1CH in Ha CH3 and is completely insoluble in water.

17 parts of the above dyestuff are heated to 100 C. in 200 parts1,2-dichlorobenzene and mixed with portions of 6.3 parts dimethylsulphate. Stirring is continued at 120 C. for a further 2 hours. Aftercooling, the dyestuff is filtered off, washed with benzene and dried.22.6 parts of a readily water-soluble powder are obtained whichdissolves with an orange-red colour. The dyestuff has the probableconstitution N mo t A) N-N=NN CHaSOt H CHa H 01 ('JH: and dyes textilematerials of polyacrylonitrile in yellowish red shades of good fastnessto wet processing and light.

The 1-(3'-chloro 4' aminophenyl)-triazole-( 1,2,3) of MP. 87 C., used inthis example as diazo component was prepared from 3-chloro-4nitroaniline by conversion into 3 chloro 4 nitrophenyl-azide andreaction of this azide in an acetone solution at 100 C., in anautoclave, with acetylene to give the 1-(3-chloro-4'-nitrophenyl)-triazole-(1,2,3) of MP. 135 C. This nitro compound was finally reducedwith iron or by catalysis to the amine.

EXAMPLE 12 A solution of 31.9 parts 3 methyl 1 (3' chloro-4-aminophenyl)-(1,2,3)-triazolium methosulphate, prepared by hydrolysis of36.1 parts 3-methyl-1(3-chloro'4'-acetylaminophenyl)-(1,2,3)-triazoliummethosulphate in a mixture of 150 parts water and 30 parts concentratedhydrochloric acid at 95100 C. for 30 minutes, is diazotised at 0-3" C.with a solution of 6.9 parts sodium nitrite in 50 parts water, and theclear diazonium salt solution is added, after removal of a small excessof nitrous acid by means of amidosulphonic acid, to a solution of 13.5parts 3-methyl-N,N-dimethylaniline in 100 parts water and partsconcentrated hydrochloric acid. The coupling resulting in the monoazodyestuff is completed by the addition of sodium acetate. The resultingdyestufi is precipitated by the addition of 40 parts sodium chloride andfiltered 01f. After drying, there are obtained 42.9 parts of a redpowder which readily dissolves in water with an orange-red colour. Thedyestuff has the probable constitution CH3 N=N N CHaS 04 Shade onExample Coupling component: polyacrylonitrile 13 N,N-diethylanilineStrongly reddish orange. 14 N-ethyl-N-cyanoethylaniline Reddish orange.15 3-chloro-N,N-diethylaniline Red.

NmethylN-phenylaniline Yellowish red. N,N:dihydroxy-ethylanilineReddisli orange. 1-amino-5-hydroxynaphthalene. Strongly bluish Bordeaux.19 1,2,3,4-tetrahyd1'o-3,7-dihydroxy- Violet.

benzo[h]quinoline. 20 1-pl1e1tyl-Bqnethyl-pyrazolonc-5.. Yellow. 21l-B-cyanoethyl-B-methyl-pyraz- D0.

clone-5 qnethyl-ind0le Reddish yellow. melthylpyrazolo[2,3-a1benzimida-Yellow.

EXAMPLE 24 The diazonium salt solution prepared according to Example 12is added at 0-10 C. to a solution of 10.7 parts S-methylaniline in 50parts water and 10 parts concentrated hydrochloric acid, and theimmediately starting coupling is completed by the addition of sodiumacetate up to a 'pH value of 45. The dyestuff is precipitated by theaddition of sodium chloride and filtered off. It is an orange colouredpowder which is dissolved in 300 parts water and parts concentratedhydrochloric acid and diazotised at 3-8 C. with a solution of 6.9 partssodium nitrite in 50 parts water. After removal of a small excess ofnitrous acid by means of amidosulphonic acid, the diazoniu-m saltsolution is added to a solution of 18.3 parts N methyl N phenylanilinein 50 parts water and 15 parts concentrated hydrochloric acid. When thecoupling at a weakly acidid pH value is completed, the precipitation ofthe dyestuff is completed by the addition of 40 parts sodium chloride.The dyestuif is filtered off and dried. It has the probable constitutionand dyes textile materials of polyacrylonitrile in redbrown shades ofvery good fastness to wet processing and very good fastness to light.

If in Example 24 there are used as intermediate component, instead of10.7 parts 3-methylaniline, 12.3 parts 3-methoxy-aniline and as endcomponent, exactly as in Example 23, 18.3 parts N methyl Nphenylaniline, then the diazo dyestutf of the following probableconstitution is obtained:

This dyestuff dyes polyacrylonitrile fibres in bluish garnet shades ofvery good fastness to wet processing and to light.

EXAMPLE 25 A solution of 28.6 parts 3-methyl-1-(3-aminophenyl)- 1,2,3triazolium methosulphate, obtained by hydrolysis of 33 parts 3 methyl 1(3-acetylaminophenyl)-1,2,3- triazolium methosulphate in a mixture of150 parts water and 30 parts concentrated hydrochloric acid at 95- 100C. for 30 minutes, is diazotised at 3 C. in the usual manner with asolution of 6.9 parts sodium nitrite in 50 parts water. The diazoniumsalt solution is added to a solution of 15.9 parts1-amino-S-hydroxynaphthalene in 300 parts water and parts concentratedhydrochloric acid. When the coupling is completed in a medium reactingacid to Congo, the resulting dyestufl? is filtered off. After drying,39.3 parts of this dyestuff are obtained in the form of a blue-blackpowder which readily dissolves in water. The dyestuff dyespolyacrylonitrile fibres from an aqueous solution in Bordeaux shades.The dyeings possess good fastness to wet processing and to light. Thedyestuff has the probable formula.

CHaSOa The 3 methyl (3' acetylaminophenyl)-1,2,3-triazoliummethosulphate (M.P. 257259 C.) employed in this example was prepared bythe reaction of 3- nitrophenylazide with acetylene at 100 C. in anacetone solution, reduction of the resulting 1 (3' nitro phenyl)-triazole-(1,2,3) of M.P. 1l2-114 C. with iron to give the 1 (3aminophenyl) triazole (l,2,3) of M.P. 121- 123 C., acetylation to the 1(3' acetylaminophenyl)- triazole-(1,2,3) of M.P. 175176 C. andquaternisation of this acetylamino compound.

EXAMPLE 26 20.4 parts 1 (3' amino 4-ethoxyphenyl)-triazole- (1,2,3) ofM.P. 121-122 C. are dissolved in 100 parts water and parts concentratedhydrochloric acid and the solution is diazotised at 0-3 C. with asolution of 6.9 parts sodium nitrite in parts water. The diazonium saltsolution is added to a solution of 17.4 parts N-ethyl-N-B-cyanoethyl-aniline in 100 parts water and 10 parts concentratedhydrochloric acid. The coupling resulting in the monoazo dyestuff iscompleted by the addition of a sodium acetate solution and the dyestufiformed is isolated by filtration. After washing with water and drying36.1 parts of this water-insoluble dyestuif are obtained in the form ofan orange-brown powder.

19.5 parts of this dried dyestuif are heated to 100 C. in 250 parts1,2-dichlorobenzene, and portions of 20.1 parts p-toluene-sulphonic acidethyl ester are then added at the same temperature. The reaction mixtureis then further stirred at 120130 C. for 2-3 hours. After cooling, theprecipitated dyestuff is filtered off and the dyestuff is washed withbenzene twice or three times. The dyestuff which is then water-solubleis, after drying, a redbrown powder; it has the probable formula C H2 CH2 C N r R mo al-- H 10 and dyes polyacrylonitrile fibres from anaqueous bath in red-orange shades.

EXAMPLE 27 The solution of 30 parts of 3-methyl-1-(3'-methyl-4'-aminophenyl)-1,2,3-triazolium methosulphate of the formula which wasobtained by saponification of 34.2 parts of 3-methyl-1-(3-methyl-4'-acetylaminophenyl) 1,2,3 triazolium methosulphatein a mixture of 150 parts of water and 30 parts of concentratedhydrochloric acid at to C. during 30 minutes, is diazotised at 0 to 3 C.with a solution of 6.9 parts of sodium nitrite in 50 parts of water andthe clear diazonium salt solution after removal of excess nitric acid bymeans of amido sulphonic acid added to a solution of 17.9 parts of3-methyl-N,N- ethyl-fi-hydroxyethyl-aniline in 100 parts of water and 10parts of concentrated hydrochloric acid. The coupling and formation ofthe monoazo dyestuff is completed by the addition of sodium acetate. Thedyestuff thus formed can be precipitated by means of 40 parts of rocksalt and filtered. After drying one obtains 50.8 parts of a red powderwhich dissolves in water with red-orange colour. The dyestuifcorresponds to the formula HaC-N=N l CH2CH2OH H3 CH3 It dyespolyacrylonitrile fabrics yellowish red shades with very good wet andlight fastness properties.

If in this example the diazo component is replaced by the equivalentamount of the diazo components listed in the following table valuablewater-soluble dyestuffs are likewise obtainable which dyepolyacrylonitrile fabrics in shades given below:

A diazoniurn salt solution prepared in accordance with the method givenin Example 12 is added at 0 to 5 C. to a solution of 17.9 parts of3-methyl-N,N-ethyl-,B-cyanoethylaniline in 100 parts of water and 10parts of concentrated hydrochloric acid. The coupling and formation ofthe monoazo dyestutf is completed by buffering the reaction medium withsodium acetate. The dyestulf thus formed is salted out, filtered withsuction and dried. One

1 l obtains 43.7 parts of the dyestufi of the following constitution:

It dyes polyacrylonitrile fabrics strongly yellowish red shades withgood fastness to light and to wet processing.

If in this example the diazo component is replaced by the equivalentamount of the diazo components listed in the following table valuablewater-soluble azo dyestuifs are likewise obtained which dyepolyacrylonitrile fabrics in the shades given below:

wherein A stands for the residue of a coupling component selected from agroup consisting of (a) aminophenyl which is unsubstituted in the phenylradical, or is substituted in the phenyl radical by at least one memberselected from the group consisting of methyl, ethyl, bromo, chloro,methoxy,

ethoxy, acetylamino, methylmercapto, and ethylmercapto, and which isunsubstituted at the N atom or is substituted at the N atom by at leastone member selected from the group consisting of lower alkyl, phenyl,hydroxyethyl, cyanoethyl, and benzyl,

(b) hydroxyphenyl which is unsubstituted or is substituted by at leastone member selected from the group consisting of methyl and chloro;

(c) hydroxynaphthalene which is unsubstituted or is substituted by anamino group;

(d) pyrazolon-(5)-yl which is substituted with at least 12 for anon-ionic substituent selected from the group consisting of hydrogen,alkyl of 1 to 4 carbon atoms, halogen atoms, trifluoroalkyl of 1 to 4carbon atoms, alkoxy of 1 to 4 carbon atoms, or alkylthioether of 1 to 4carbon atoms; and X stands for an anion, said dyestufi being free ofsulfonic acid groups.

2. An azo dyestuff of claim 1 of the formula (R Zym wherein R' standsfor CH or C H R stands for C1 or methoxy or ethoxy, R stands forhydrogen, Cl, Br, CH C H CH O, C H O, CH3S or C H S, m' strands for thenumber 0 or 1, B stands for the residue of a coupling componentconsisting of an aminobenzene radical (a) of claim 1 and X stands for ananion.

3. A dyestufi" of claim 1 of the formula R112 wherein R' stands for CHor C H R" stands for hydrogen or D stands for one of the residues or1-phenyl-3-methyl-5-pyrazolone bound to the azo group in 4-position or Rstands for lower alkyl or hydroxy lower alkyl, R;

stands for lower alkyl, hydroxy lower alkyl or cyano lower alkyl, Rstands for hydrogen, methyl or acetyl amino, R stands for lower alkyland X is an anion.

4. A dyestufl? of claim 1 of the formula CHsSOF 5. A dyestufi' of claim1 of the formula one member selected from the group consisting ofmethyl, phenyl, cyanoethyl, and hydroxyethyl;

(e) Z-methyl-pyrazolo 2,3-a] benzimidazolyl;

(f) 2-methyl-pyrazolo [3,2-b] quin azolyl;

(g) Z-methyl-indolyl;

(h) 1,3-dihydroxy-isoquinolyl;

(i) tetrahydrobenzoquinolyl substituted by at least one hydroxy group;

(j) tetrahydroquinolyl which contains at the N atom a substituentselected from the group consisting of ethyl and ethoxycarbonylethoxyradicals; and wherein B is selected from (a) as defined above; wherein nis 0 or 1 and m is 0, 1 or 2; R stands for alkyl containing 1 to 4carbon atoms or benzyl; R stands H: CH3

6. A dyestuff of claim 1 of the formula eHs 7 A dyestufi' of claim 1 ofthe formula CH3N N CHzCHzOH (lll $113 CH2CH2OH

